WO2007088814A1 - Toner for developing electrostatic image - Google Patents

Abstract

Disclosed is a toner for developing electrostatic images which is excellent in storage stability and fixability at low temperatures. This toner for developing electrostatic images is capable of maintaining high fixing ratio even at low fixing temperatures. Specifically disclosed is a toner for developing electrostatic images which contains colored resin particles containing a binder resin, a coloring agent and a mold release agent. This toner for developing electrostatic images is characterized in that the mold release agent is composed of an aliphatic hydrocarbon polymer obtained by polymerizing an aliphatic hydrocarbon monomer.

Description

 Specification

 Toner for electrostatic image development

 Technical field

 The present invention relates to an electrostatic charge image developing toner that can be used for developing an apparatus using electrophotography such as a copying machine, a facsimile machine, and a printer.

 Background art

 In an image forming apparatus using electrophotography, such as a copying machine, a facsimile machine, and a printer, an electrostatic latent image formed on a photoreceptor is firstly charged with an electrostatic charge image developing toner (hereinafter simply referred to as “static toner”). The toner image developed and then formed on the recording material such as paper is fixed by various methods such as heating, pressurization, and solvent vapor. An image is formed.

 In recent years, these image forming apparatuses have been required to reduce energy consumption and print speed. In the electrophotographic image forming process, a process that consumes a lot of energy is a process of fixing toner onto a recording material (fixing process). As a fixing method, a method of fixing by heating and pressing with a fixing roll is generally used. In this method, it is usually necessary to raise the temperature of the fixing roll at the time of fixing. The ability to lower the temperature of the fixing roll during fixing is required from the viewpoint of energy saving. In addition, the fact that fixing at a low temperature can cope with high-speed printing also requires a reduction in the temperature of the fixing roll at the time of fixing from the viewpoint of a demand for high speed.

 As the toner, a toner having a low minimum fixing temperature is required. In order to obtain a toner excellent in low-temperature fixability, conventionally, a method of lowering the glass transition temperature of the toner, a method of adding a low melting point or low molecular weight resin, etc., a low softness having releasability such as a wax.匕 A method for incorporating a substance into the toner has been proposed!

 [0005] On the other hand, as a characteristic contrary to low-temperature fixability, toner storage stability is required.

The storability is a characteristic that indicates that toner aggregation (blocking) hardly occurs when the toner is stored at a high temperature. This characteristic is a special characteristic necessary to prevent the toner from aggregating when the temperature inside the printer rises due to heat generated by fixing during toner transportation or printing. It is sex.

 [0006] Techniques relating to a waxy wax added to a toner that solves the above-mentioned required problems have been proposed.

 Patent Document 1 describes that R, CH = CH2 (R,: carbon) having a DSC melting point of 70 to 130 ° C, a molecular weight Mn of 100 to 25,000, and a molecular weight distribution MwZMn of 1.5 to 3.0. A toner containing 1-olefin polymer represented by 1-olefin linker represented by the formula (1 to 28 alkyl) is also proposed (Claim 1), and the DSC melting point is 81 ° C. Toners containing polypropylene wax at ˜120 ° C. are disclosed.

 [0007] In addition, Patent Document 2 discloses that a toner particle (colored resin particle) having a colorant and binder resin is also polymerized with a polymer wax obtained by polymerizing oc-olefin having 19 to 60 carbon atoms and a crystal. A solid toner for wet development dispersed in an electrically insulating medium containing a wax has been proposed.

 [0008] However, as a result of investigations by the present inventors, the toner described in Patent Document 1 is a toner that maintains the conventional storability when used in a recent color printer. However, the low-temperature fixability was still insufficient to meet the demand for improved low-temperature fixability. A polymer wax obtained by polymerizing a-olefin described in Patent Document 2 is intended to be used as a solid toner medium (that is, a toner matrix) for wet imaging. When used as a component contained in the toner, there is a problem that the storage stability of the toner is lowered.

 In addition, as a characteristic contrary to low-temperature fixability, toner printing durability is also required. Print durability is a characteristic that can maintain print quality such as image quality even when many sheets are printed. In the toner cartridge, it is required that the toner is less deteriorated due to the stress that the toner receives from the printing of a large number of sheets. In particular, the printing durability is such that no capri is generated during continuous printing. You are asked to make it.

[0009] Further, with the spread of color image formation in recent years, the required quality for the color toners used therein has become higher, and even for properties that are contrary to low-temperature fixability, further improvement is required. There is a need for improvement. In particular, there is a demand for a toner that has good printing durability even after being exposed to high temperatures during transportation or in printing in a high temperature environment. Various proposals have been made to solve the above-mentioned problems while satisfying the requirements for low-temperature fixability.

 [0010] In Patent Document 3, the melting point is 60 to 85 ° C as a release agent at 25 ° C for the purpose of obtaining a toner excellent in both low-temperature fixability and printing durability. An electrostatic charge image developing toner containing paraffin wax having a penetration force of ˜10 is disclosed. However, when the release agent described in Patent Document 3 is used, the printing durability after high-temperature storage is greatly deteriorated.

 [0011] Patent Document 4 aims to obtain a toner excellent in both low-temperature fixability and storage stability, and binds waxes having a heat absorption range by DSC of only 50 ° C or higher as a binder resin. An electrostatic charge image developing toner containing 1 to 15 parts by weight based on the weight part is disclosed. Here, the wax used is a product obtained by removing and purifying a portion of the ester power DSC endothermic region of 50 ° C or less between fatty acid and alcohol. However, even when the wax described in Patent Document 4 is used, printing durability under high temperature storage deteriorates.

 [0012] Patent Document 5 discloses a toner produced by an emulsion polymerization agglomeration method, which contains a wax having a penetration force of less than or equal to the ester component as a main essential component and a melting point of 60 to 110 ° C. Proposed. However, the toner of Patent Document 5 has been insufficient for the required level of both low-temperature fixability and high storability and printing durability with the recent spread of color printers.

 Patent Document 6 aims at obtaining a toner excellent in all of low temperature fixing property, storage property, printing durability, particularly printing durability under high temperature storage. An electrostatic charge image developing toner containing colored rosin particles containing a specific ester compound is disclosed. The ester compound described in Patent Document 6 has an endothermic peak of 65 ° C or higher in the DSC curve, an endothermic value at a temperature 20 ° C lower than the endothermic peak temperature, and A (mW). When the endotherm at a temperature 50 ° C lower than the peak temperature is B (mW), the number of ester bonds is C, and the amount of ester compound used as a measurement sample is D (mg), It is characterized by satisfying the relationship expressed by

 Relational expression: 0≤ I A-B I / (C X D) ≤0.02

However, even when the ester compound described in Patent Document 6 is used, high Printing durability after storage at low temperature is lower than printing durability before storage at high temperature.

 [0014] Further, the toner characteristics required in addition to the low-temperature fixability, storage stability and printing durability include offset resistance. Offset resistance is a characteristic that indicates the wide temperature range in which fixing is possible. Particularly for toners that can be fixed at low temperature, it is necessary to obtain stable print quality even if the temperature of the fixing roll is wide, and therefore it is required that the toner does not fuse to the fixing roll even at a high fixing temperature. Being

 Patent Document 7 contains ester wax (corresponding to “low molecular weight wax”) and hydrocarbon wax (corresponding to “aliphatic hydrocarbon polymer”) having a melting point in the temperature range of 55 to 120 ° C. However, there is disclosed a toner characterized in that the melting point of the ester wax is lower (claim 1), and the weight average molecular weight (Mw) of the ester wax is 350 to 1,500. It is described that the weight average molecular weight (Mw) is 300 to 4,000 (claims 3 and 4).

 [0015] Patent Document 8 discloses polyester as a binder resin and ester wax as a release agent.

 (Corresponding to “low molecular weight wax”) and petroleum wax (corresponding to a part of paraffin wax “aliphatic hydrocarbon polymer”) are disclosed (claims 1 and 2), In addition, it is described that the melting point of the petroleum wax is preferably 70 ° C. or more, and the molecular weight of the ester wax and the petroleum wax is described. /.

 [0016] Patent Document 9 is obtained by polymerizing a monomer in the presence of a high melting point wax (polyethylene wax (corresponding to "aliphatic hydrocarbon polymer")) having a melting point of 75 to 140 ° C. An electrophotographic toner is disclosed, which comprises the obtained ox-containing resin and a low-melting wax having a melting point of 50 to 90 ° C. (ester wax (corresponding to “low molecular weight status”)). Claims 1 to 3) and the molecular weights of ester wax and polyethylene wax are not described.

 [0017] However, the toners of Patent Documents 7 to 9 have a high level of offset resistance and printing durability while maintaining a high balance between low-temperature fixability and storage stability. It was insufficient to meet the demand level.

 [0018] Patent Document 1: JP 2000-352838 A

Patent Document 2: JP-A-9 106113 Patent Document 3: Japanese Patent Laid-Open No. 2005-266753

 Patent Document 4: Japanese Patent Laid-Open No. 3-91764

 Patent Document 5: JP 2000-35690 A

 Patent Document 6: JP-A-2005-221571

 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-251932

 Patent Document 8: Japanese Unexamined Patent Publication No. 2005-141189

 Patent Document 9: Japanese Patent Laid-Open No. 2003-5431

 Disclosure of the invention

 Problems to be solved by the invention

[0019] The present invention has been accomplished in view of the above-mentioned actual situation, and the first object thereof is low-temperature fixability that is excellent in toner storage stability, low, high at a fixing temperature, and capable of maintaining a fixing rate. It is an object of the present invention to provide an electrostatic charge image developing toner excellent in the above.

 A second object of the present invention is to provide a toner for developing an electrostatic charge image that has excellent storage stability and printing durability without impairing low-temperature fixability, and particularly excellent printing durability after high-temperature storage.

 Furthermore, a third object of the present invention is to provide a toner for developing an electrostatic charge image that balances the storage stability and low-temperature fixability of the toner and is excellent in offset resistance and printing durability.

 Means for solving the problem

[0020] As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using an electrostatic charge image developing toner containing colored rosin particles containing a specific aliphatic hydrocarbon polymer. .

 [0021] That is, according to the present invention, in the toner for developing an electrostatic charge image containing colored resin particles containing a binder resin, a colorant, and a release agent, the release agent is an aliphatic hydrocarbon. It is possible to provide an electrostatic charge image developing toner characterized by being an aliphatic hydrocarbon polymer obtained by polymerizing monomers.

Further, the melting point (TmD) of the aliphatic hydrocarbon polymer is preferably less than 80 ° C. [0022] Specifically, in the electrostatic image developing toner according to the first invention, the release agent is

 (1) DSC curve by differential scanning calorimeter (DSC) has one melting point (TmD) defined as the temperature at the top of the peak, and

 (2) The full width at half maximum of the peak is within 12 ° C

 (3) It is an aliphatic hydrocarbon polymer.

 [0023] Further, in the electrostatic image developing toner according to the second invention, the release agent is

 (1) Penetration at 25 ° C (JIS K2235-1991) force or less, and

 (2) Solubility in toluene at 25 ° C is 5-60% by weight

 (3) It is an aliphatic hydrocarbon polymer.

 In this case, the melting point (TmD) of the aliphatic hydrocarbon polymer is preferably 40 ° C. or higher and lower than 80 ° C.

 Furthermore, in the electrostatic image developing toner according to the third invention, the release agent is

 (1) Melting point (TmD) is 70 ° C or less, and

 (2) Penetration at 25 ° C (JIS K2235-1991) is 3 or less

 (3) It is an aliphatic hydrocarbon polymer.

 In this case, the weight average molecular weight of the aliphatic hydrocarbon polymer is 10,000 or more and 100,000 or less.

 The aliphatic hydrocarbon polymer is preferably a higher a-olefin polymer obtained by polymerizing an oc single-year-old olefin monomer having 10 or more carbon atoms. The higher a-olefin polymer is preferably used as a catalyst. It may be a polymer that is polymerized in the presence of a sensing compound. The α-olefin monomer has more preferably 16 or more carbon atoms.

 Other release agents can be used in combination with the aliphatic hydrocarbon polymer. Furthermore, in the electrostatic image developing toner according to the fourth invention, the release agent is

 (1) an aliphatic hydrocarbon polymer having a peak top molecular weight of 10,000 or more and a melting point of 70 ° C or less, and

 (2) Low molecular weight wax with a peak top molecular weight of 5,000 or less

 It is characterized by being.

The low molecular weight wax is preferably an ester wax. In this case, the melting point (TmD) of the aliphatic hydrocarbon polymer is preferably not more than the melting point (TmD) of the low molecular weight wax. The content ratio of the aliphatic hydrocarbon polymer to the low molecular weight wax (the content of the aliphatic hydrocarbon polymer Z the content of the low molecular weight wax) is preferably 98Z2 to 25Z75.

 According to the present invention, the colored resin particles can be produced by a wet method. In addition, the colored resin particles preferably have a core-shell type structure.

 The invention's effect

 [0024] According to the present invention, there is provided a toner for developing an electrostatic charge image that has excellent storage stability and low toner, and excellent low-temperature fixability that can maintain a high fixing rate even at a fixing temperature.

 In addition, according to the present invention, there is provided a toner for developing an electrostatic charge image that is excellent in storage stability and printing durability without impairing low-temperature fixability, in particular, printing durability after high-temperature storage.

 Furthermore, according to the present invention, there is provided a toner for developing an electrostatic charge image that balances the storage stability and low-temperature fixability of the toner, and is excellent in offset resistance and printing durability.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the toner for developing an electrostatic charge image of the present invention and the production method thereof will be described.

The toner for developing an electrostatic image of the present invention (in the present invention, “toner for developing an electrostatic image” is also simply referred to as “toner”) contains colored resin particles. ing. The colored resin particles contain a binder resin and a colorant, and further contain an aliphatic hydrocarbon polymer obtained by polymerizing an aliphatic hydrocarbon monomer as a release agent. Further, if necessary, it may contain other additives such as a charge control agent.

 [0027] As specific examples of the binder resin, it has been widely used in toners such as bules such as polystyrene and styrene butyl acrylate copolymer, polyester resin, epoxy resin, and cyclized isoprene rubber. Can be mentioned. The number average molecular weight of the binder resin is not particularly limited. Usually, it is 2,000 to 50,000, preferably <3,000 to 3,000,000.

[0028] As the colorant, various pigments and dyes used in the toner field can be used. When producing a color toner, in addition to black and white, cyan, yellow, and magenta colorants can be used. [0029] Black colorants include carbon black, titanium black, and -grosine-based dyes and pigments; conoleto, nickel, magnetite, iron trioxide, manganese iron oxide, iron oxide zinc, and Pigments such as magnetic powder such as nickel oxide iron; and the like can be used. Carbon black having a primary particle size of 20 to 40 nm is preferably in this range, so that the strong black black can be uniformly dispersed in the toner and the capri is reduced.

 As a white colorant, titanium white or the like can be used.

 [0030] Examples of cyan colorants include copper phthalocyanine compounds, derivatives thereof, anthraquinone compounds, and the like, CI pigment blue 2, 3, 15, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 16: 1, 60, etc.

 [0031] Yellow colorants include monoazo pigments, azo pigments such as disazo pigments, and compounds such as condensed polycyclic pigments. CI pigment yellow 3, 12, 13, 13, 14 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, and 213 It is mentioned with equal power.

 As the magenta colorant, compounds such as monoazo pigments, azo pigments such as disazo pigments, and condensed polycyclic pigments are used. Specifically, CI Pigment Red 31, 48, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 170, 184, 185, 187, 202, 206, 207, 209, 251 and CI Pigment Violet 19 etc.

 [0033] The amount of each colorant is usually 1 to 50 parts by weight, preferably 100 parts by weight of the binder resin.

 It is preferably 1-20 parts by weight.

In the present invention, in order to obtain a toner having a low level of toner storage stability and a minimum fixing temperature, that is, a low-temperature fixing property at a high level, the above-mentioned specific aliphatic hydrocarbon is used as a release agent. A polymer is used.

The aliphatic hydrocarbon polymer used in the present invention is obtained by polymerizing an aliphatic hydrocarbon monomer that is a hydrocarbon that does not contain an aromatic ring among hydrocarbons composed of only carbon atoms and hydrogen atoms. It is a polymer. The aliphatic hydrocarbon polymer preferably has a melting point (TmD) of less than 80 ° C. Beyond this range, the resulting toner is poorly stored and tends to adhere. Here, the melting point is measured by a differential scanning calorimeter (DSC). The measurement of the aliphatic hydrocarbon polymer by a differential scanning calorimeter (DSC) is performed in accordance with ASTM D3418-82, and a commercially available differential scanning calorimeter can be used. As a commercially available differential scanning calorific value, for example, a differential scanning calorimetric analyzer (trade name: RDC-220, manufactured by Seiko Instruments Inc.) can be used. The measurement is performed under the condition that the temperature is increased from 20 ° C to 100 ° C in 10 ° CZ minutes.

[0035] (First invention)

 Since such a release agent is an (3) aliphatic hydrocarbon polymer having the following characteristics (1) and (2), a toner having excellent storage stability and excellent low-temperature fixability can be obtained. it can.

 (1) In the DSC curve by the differential scanning calorimeter (DSC), it has one melting point (TmD) defined as the temperature at the top of the peak.

 (2) The full width at half maximum of the peak is within 12 ° C.

 (3) An aliphatic hydrocarbon polymer having the characteristics (1) and (2).

 [0036] The aliphatic hydrocarbon polymer used in the present invention has one melting point (TmD) defined as the temperature at the top of a peak in a DSC curve by a differential scanning calorimeter (DSC). The full width at half maximum of the peak is within 12 ° C. The full width at half maximum of the peak is preferably within 10 ° C, more preferably within 8 ° C. Beyond this range, the resulting toner is poorly stored and becomes fuzzy. The melting point (TmD) is preferably 40 ° C or higher and lower than 80 ° C, more preferably 45 ° C or higher and lower than 70 ° C, more preferably 50 ° C or higher and lower than 65 ° C. Note that the higher α-olefin polymer of the present invention has one peak as described above in the DSC curve. This single peak may have a shoulder, but preferably has a shoulder.

[0037] Specific materials that can be used as the aliphatic hydrocarbon polymer include, for example, paraffin nitrogen, microcrystalline wax, Fischer-Tropsch wax, a one-year-old refin polymer, and other waxes. In particular, many higher α-olefin polymers have the above properties. [0038] Among them, a higher a-olefin polymer obtained by polymerizing an a-olefin monomer having 10 or more carbon atoms is preferable, more preferably it has 16 or more carbon atoms, and more preferably 1 It is 8 or more and 24 or less, and particularly preferably 22 or more and 24 or less. When the carbon number is within the above range, it is easy to obtain a specific higher α-olefin polymer in the present invention. If the carbon number exceeds this range, the resulting toner may be inferior in low-temperature fixability, and if it is less than this range, storage stability may be problematic. Further, the a-olefin monomer is preferably purified by a method such as distillation.

 [0039] Specific examples of such preferable α-olefin monomers include 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- Heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henecocene, 1-dosecene, 1-tricosene, 1-tetracosene, 1 pentacosene, 1-hexacocene, etc. 1-tetracosene, 1 monohexacocene.

 [0040] The higher α-olefin polymer in the present invention has a weight average molecular weight Mw of 15,000 to L: 10,000, preferably <20,000 to 100,000, more preferably ^ /! The molecular weight distribution MwZMn represented by the ratio of Mw to the number average molecular weight Mn is preferably 1.5 to 3.0, more preferably 1.6 to 2.8.

 In the present invention, the weight average molecular weight Mw, the number average molecular weight Mn, and the peak top molecular weight Mp are polystyrene equivalent molecular weights measured by gel permeation chromatography (GPC) method, and specifically, Thus, it can be measured.

 The measuring device is a GPC measuring device (trade name: Alliance GPC2000, manufactured by Waters). In addition, the sample solution to be injected is lmgZml for polymer and 0.5 mgZml for wax, and 1,2,4 trichlorodiethylbenzene solution (including 300ppm of dibutylhydroxytoluene) with a 0.5μm membrane filter. After filtration, 240 μ 1 of the filtrate was used. The column was a mixed polystyrene gel column (trade name: GMHHR—H (S) HT, manufactured by Tosoichi Co., Ltd.), column temperature 145 ° C, flow rate 1. Obtain by measuring under the condition of OmlZmin. For detection, use an infrared detector and a wavelength of 3.41 μm.

[0041] In order to obtain a higher a-olefin polymer, the polymerization of the a-olefin monomer is used as a catalyst. It is preferable to be performed in the presence of Metaguchi Sen compound.

 Examples of the metacene compound include dimethylsilylene bis (2-methyl-4,5 benzoin dur) zirconium dichloride, dimethylsilylene bis (2-methyl 4-phenol indur) zirconium dichloride, dimethylsilylene bis (2-methyl 4naphthyl). Ndenyl) zirconium dichloride, dimethylsilylenebis (2-methylindul) zirconium dichloride, ethylenebis (2-methylindulur) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (3 trimethylsilylmethyl-indul) zirconium dichloride, (1,2, -dimethylsilylene) (2,1, -dimethylsilylene) (3-trimethylsilylmethyl-indul) (indul) zirconium dichloride, (1, 2'—Dimethi Silylene) (2,1'-Dimethylsilylene) bis (indul) dirucum-dichloride, (1,2,1-dimethylsilylene) (2,1,1-dimethylsilylene) bis (3-n-butyl-indul) Zirconium dichloride, (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) (n-butyl-indur) (indur) zirconium dichloride, (1, 2, -dimethylsilylene) (2, 1, — Dimethylsilylene) bis (indul) zirconium dichloride, 1,1,1-dimethylsilylenebis (2 ethyl-4 (2 fluoro-4-biphenyl) -4H-azulenyl) zirconium dichloride, and dimethylsilylene (cyclopentadiene) -L) (2,4 dimethyl-4H-1 azule) zirconium dichloride compounds such as zirconium dichloride, and these Zirconium compounds such as compounds in which the dichloride of the zirconium dichloride compound is substituted with dimethyl or dibenzyl; and titanium compounds in which the zirconium of these zirconium compounds is substituted with titanium; and the like.

 The above-mentioned meta-mouth compound may be used alone or in combination of two or more. Furthermore, as the catalyst, in addition to the metacene compound, an organic aluminum compound such as triisobutylaluminum, or an organic boron compound such as dimethylaminotetrakispentafluorophenolate is used. It is preferable to obtain an OC-olefin polymer having the above characteristics.

The amount of the aliphatic hydrocarbon polymer is 1 to 50 parts by weight with respect to 100 parts by weight of the binder resin. Preferably there is. If the amount of the aliphatic hydrocarbon polymer is smaller than the above range, the low temperature fixing property

 If the amount of the improvement effect is lower than the above range, the printing durability is deteriorated.

 In the present invention, other release agents may be used in combination with the aliphatic hydrocarbon polymer.

. Examples of the release agent to be used in combination include molecular end oxidized low molecular weight polypropylene, low molecular weight end-modified polypropylene in which the molecular end is substituted with an epoxy group, and a block polymer of these and low molecular weight polyethylene, molecular end acid and low molecular weight polyethylene, End-modified polyolefin waxes such as low molecular weight polyethylenes whose molecular ends are substituted with epoxy groups and block polymers of these with low molecular weight polypropylene; Candelilla, Carnauba

, Rice, wax, jojoba and other natural waxes; pentaerythritol esters such as pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, pentaerythritol tetralaurate; dipentaerythritol hexamyristate, dipentaerythritol Dipentaerythritol, such as oxapalmitate, dipentaerythritol hexalaurate; Tonoles Estenole; Hexaglycerone ester, such as Hexaglycerono lectobenenate; Or two or more types are exemplified.

[0044] In the present invention, the production method of the colored resin particles includes a dry method such as a pulverization method and a wet method such as an emulsion polymerization aggregation method, a dispersion polymerization method, a suspension polymerization method, and a dissolution suspension method. It is easy to obtain a toner excellent in printing characteristics such as image reproducibility, and the wet method is preferred. Among them, the polymerization method such as the emulsion polymerization aggregation method, the dispersion polymerization method, and the suspension polymerization method has a relatively small particle size distribution in the microorder, and thus the more preferable suspension polymerization method is more preferable.

 [0045] As the wet method, the emulsion polymerization aggregation method polymerizes emulsified polymerizable monomers to obtain resin particles, and aggregates them with a colorant or the like to produce colored resin particles. In the dissolution suspension method, a solution in which a toner component such as a binder resin colorant is dissolved or dispersed in an organic solvent is formed into droplets in an aqueous medium, and the organic solvent is removed to form colored resin particles. It is a manufacturing method, and a publicly known method can be used for each.

[0046] Colored resin using a suspension polymerization method, which is a more preferable method for producing the toner of the present invention. When the particles are manufactured, the following process is performed. First, a polymerizable monomer, a colorant, and an aliphatic hydrocarbon polymer as a release agent, and further, if necessary, other additives such as a charge control agent are mixed to obtain a polymerizable monomer composition. To do. After this polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer, droplet formation is performed. Thereafter, polymerization is carried out in the presence of a polymerization initiator to obtain an aqueous dispersion of colored resin particles. This water dispersion is washed, dehydrated and dried to obtain dried colored resin particles. The dried colored resin particles are classified as necessary, mixed with an external additive, and a carrier is further added as necessary to obtain a toner.

 [0047] The polymerizable monomer is a main component serving as a binder resin and refers to a polymerizable compound.

 In the aforementioned components such as the colorant, the weight of the binder resin, which is the standard of the amount, can be replaced with the weight of the polymerizable monomer that is substantially equal to the weight of the polymerizable monomer.

 As the main component of the polymerizable monomer, it is preferable to use a monobule monomer. Monovinyl monomers include styrene; styrene derivatives such as butyltoluene and α-methylstyrene; acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid Acrylic esters such as 2-ethylhexyl and dimethylaminoethyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and dimethylamino methacrylate Methacrylic acid esters such as ethyl; amide compounds such as acrylamide and methacrylamide; olefins such as ethylene, propylene and butylene; halogenated and halogenated vinylidenes such as butyl chloride, vinylidene chloride and fluorinated butyl; Butyl acetate and Bull esters such as bion pionate; bull ethers such as bull methyl ether and buretyl ether; beer ketones such as bull methyl ketone and methyl isopropyl ketone; 2 bulpyridine, 4 bull pyridine, and Ν— And nitrogen-containing bull compounds such as bull pyrrolidone. These monobule monomers may be used alone or in combination. Of these, styrene, styrene derivatives, acrylic acid esters and methacrylic acid esters are suitably used as the monomer for monomers.

[0048] The monovinyl monomer is obtained by polymerizing the monovinyl monomer. (represented as g) is preferably 80 ° C or lower. By using a monobule monomer alone or in combination of two or more, the Tg of the polymer can be adjusted to a desired range.

 [0049] In order to improve hot offset, it is preferable to use an arbitrary cross-linkable monomer together with the monobule monomer as a part of the polymerizable monomer. The crosslinkable monomer means a monomer having two or more polymerizable functional groups. Examples of the crosslinkable monomer include aromatic divinyl compounds such as dibutene benzene, divinyl naphthalene, and derivatives thereof; unsaturated polycarboxylic acid esters of polyhydric alcohols such as ethylene glycol dimetatalylate and diethylene glycol dimetatalylate. N, N-dibulaline, and other divinyl ichigo compounds such as dibule and ter; compounds having three or more vinyl groups; and the like. These crosslinkable monomers can be used alone or in combination of two or more. The crosslinkable monomer is desirably used in a proportion of 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, with respect to 100 parts by weight of the monovinyl monomer.

 [0050] Furthermore, it is preferable to use a macromonomer as a part of the polymerizable monomer because the balance between the storage stability and low-temperature fixability of the toner obtained is improved. The macromonomer has a polymerizable carbon-carbon unsaturated double bond at the end of the molecular chain, and is a reactive oligomer or polymer having a number average molecular weight of 1,000 to 30,000. The macromonomer is preferably one that gives a polymer having a higher Tg than the Tg of the polymer obtained by polymerizing only the monobule monomer. The amount of the macromonomer is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the monobule monomer. .

 [0051] In the present invention, the colored resin particles preferably contain a charge control agent. When producing a negatively charged toner, a negatively chargeable charge control agent is mainly used, and when producing a positively charged toner, a positively chargeable charge control agent is mainly used. You can also use a small amount of a charge control agent with a polarity opposite to that of the charge control agent used.

[0052] Examples of positively chargeable charge control agents include charge-controlling resins such as polyamine resins, quaternary ammonium group-containing copolymers, and quaternary ammonium salt group-containing copolymers; Imidazole compounds, Niguguchishin dyes, quaternary ammonium salts, and triaminotrimethane compounds Etc.

 Examples of negatively chargeable charge control agents include charge control of sulfonic acid group-containing copolymers, sulfonate group-containing copolymers, carboxylic acid group-containing copolymers, and carboxylate group-containing copolymers. Examples include resin, azo dyes containing metals such as Cr, Co, Al, and Fe, metal salicylates, and metal alkylsalicylates.

 In the present invention, it is preferable to use a charge control resin as the charge control agent because the printing durability of the toner becomes good. When the charge control resin is used, its addition amount is usually 0.01 to 30 parts by weight, preferably 0.3 to 25 parts by weight with respect to 100 parts by weight of the binder resin.

 [0053] In the polymerization of the polymerizable monomer, it is preferable to use a molecular weight modifier as another additive. Examples of molecular weight modifiers include mercaptan compounds such as t-decyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2, 2, 4, 6, 6 pentamethylheptane 4-thiol.

 [0054] The polymerizable monomer composition obtained as described above is dispersed in an aqueous medium containing a dispersion stabilizer, and after adding a polymerization initiator, a solution of the polymerizable monomer composition is obtained. Perform droplet formation. The method of forming the droplet is not particularly limited. For example, an in-line type emulsifying disperser (manufactured by Ebara Seisakusho, trade name: Ebara Milda), high-speed emulsifying disperser (manufactured by Tokushu Kika Kogyo Co., Ltd., trade name: TK homomixer MARK Use a device capable of strong agitation such as type II).

 [0055] The aqueous medium may be water alone! / ヽ, but a solvent that is soluble in water such as lower alcohol and lower ketone may be used in combination.

A dispersion stabilizer is contained in the aqueous medium. Examples of dispersion stabilizers include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; phosphates such as calcium phosphate; aluminum oxide, titanium oxide, and the like. Metal oxides; Metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; Water-soluble polymers such as polybutyl alcohol, methylcellulose, and gelatin; And organic compounds such as surfactants such as surfactants, cationic surfactants, non-ionic surfactants, and amphoteric surfactants. The above dispersion stabilizers can be used alone or in combination of two or more. Above all In addition, a dispersion stabilizer containing a metal compound, particularly a colloid of a poorly water-soluble metal hydroxide, can narrow the particle size distribution of the colored resin particles, and the residual amount of the dispersion stabilizer after washing is small. It is preferable that the obtained toner can reproduce an image clearly and does not deteriorate environmental stability.

 [0056] Polymerization initiators used for polymerization of the polymerizable monomer composition include potassium persulfate and persulfates such as ammonium persulfate; 4, 4, azobis (4 cyanoberic acid), 2,

2, -azobis (2-methyl-N- (2-hydroxyethyl) propionamide, 2,2, -azobis (2amidinopropane) dihydrochloride, 2,2,1azobis (2,4 dimethylvalero nitrile), and 2, 2, 2-azobisisobuty-tolyl, etc .; di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxide 2-ethyl hexanoate, t-hexyloxy 2-ethylhexanoate, Examples thereof include organic peroxides such as t-butyl peroxypiperate, diisopropyl peroxydicarbonate, di-t-butyl peroxyisophthalate, and t-butyl peroxyisopropylate. It is also possible to use a redox initiator that combines a reducing agent and a reducing agent. Door can be, since it may be durability, it is preferable to use an organic peroxide Sani 匕物,.

 As described above, the polymerization initiator is used after the polymerizable monomer composition is dispersed in the aqueous medium.

It may be added before the droplet formation, but it may be added to the polymerizable monomer composition.

[0057] The addition amount of the polymerization initiator used for the polymerization of the polymerizable monomer composition is preferably 0.1 to 20 parts by weight, more preferably 0 to 100 parts by weight of the monovinyl monomer. . 3

To 15 parts by weight, most preferably 1.0 to 10 parts by weight.

[0058] As described above, droplets of the polymerizable monomer composition are formed! / ヽ, and the aqueous medium containing the droplets of the obtained polymerizable monomer composition is heated to perform polymerization. Starting, a water dispersion of colored resin particles is obtained.

 The polymerization temperature of the polymerizable monomer composition is preferably 50 ° C or higher, more preferably 60 to 95 ° C. The polymerization reaction time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

[0059] The colored resin particles may be used in the toner as they are, but the colored resin particles are used as a core layer. In addition, it is preferable to form colored resin particles having a so-called core-shell structure obtained by forming a shell layer different from the core layer on the outer side. Colored resin particles with a core-shell structure cover the core layer made of a material with a low softening point with a material having a higher softening point, thereby lowering the minimum fixing temperature (low temperature fixability) and during storage. It is possible to balance anti-aggregation (preservability).

 [0060] The method for producing the colored resin particles having the core-shell structure using the colored resin particles obtained by the polymerization method described above can be produced by a conventionally known method with no particular limitation. In situ polymerization and phase separation are preferred from the viewpoint of production efficiency.

 [0061] A method for producing core-shell structured colored resin particles by an in situ polymerization method will be described below. In order to form a shell layer in an aqueous medium in which colored resin particles obtained by the polymerization method are dispersed. By adding a polymerizable monomer (polymerizable monomer for shell) and a polymerization initiator, and polymerizing, a colored resin particle having a core-shell structure can be obtained.

[0062] As the polymerizable monomer for the shell, those similar to the monovinyl monomer described above can be used. Among them, it is preferable to use monomers such as styrene, acrylonitrile, and methylmethacrylate which can produce a polymer having a Tg force exceeding 0 ° C. alone or in combination of two or more.

 [0063] Polymerization initiators used for the polymerization of the polymerizable monomer for shell include potassium persulfate and persulfate metal salts such as ammonium persulfate; 2, 2, -azobis (2-methyl-N- ( Azo compounds such as 2-hydridochichetil) propionamide) and 2,2, -azobis- (2-methyl-N- (1,1-bis (hydroxymethyl) 2-hydroxyethyl) propionamide); And water-soluble polymerization initiators such as The amount of the polymerization initiator is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer for shell.

 [0064] The aqueous dispersion of colored resin particles obtained by polymerization is subjected to filtration, washing to remove the dispersion stabilizer, dehydration, and drying after the completion of the polymerization. Thus, colored rosin particles can be obtained.

[0065] In the above washing method, an inorganic compound such as an inorganic hydroxide is used as a dispersion stabilizer. When used, it is preferable to dissolve and remove the dispersion stabilizer in water by adding an acid or an alkali to the aqueous dispersion of the colored resin particles. When a colloid of a poorly water-soluble inorganic hydroxide is used as the dispersion stabilizer, it is preferable to add an acid to adjust the pH of the colored resin particle aqueous dispersion to 6.5 or lower. As the acid to be added, inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as formic acid and acetic acid can be used.

 [0066] The methods of dehydration and filtration are not particularly limited, and various known methods can be used. Examples thereof include a centrifugal filtration method, a vacuum filtration method, and a pressure filtration method. Also, the drying method is not particularly limited, and various methods can be used.

 [0067] When producing colored rosin particles by employing a pulverization method which is a dry method, the following process is performed. Specifically, first, a binder resin, a colorant, an aliphatic hydrocarbon polymer, and, if desired, a charge control agent are further mixed in a mixer such as a ball mill, a V-type mixer, a Henschel mixer, a high-speed dissolver, an internal mixer. Etc. to mix. Next, the mixture obtained as described above is kneaded while being heated using a pressurizer, a single screw extruder kneader, a twin screw extruder kneader, a roller or the like. The obtained kneaded material is coarsely pulverized using a pulverizer such as a hammer mill, a cutter mill, or a roller mill. Further, after finely pulverizing using a pulverizer such as a jet mill and a high-speed rotary pulverizer, the particles are classified to a desired particle size by a classifier such as an air classifier and an airflow classifier, and colored by a pulverization method Obtain rosin particles. As the colorant used in the pulverization method and the charge control agent used as required, those listed in the above-mentioned polymerization method can be used. This is the same part by weight obtained by replacing 100 parts by weight of the nobilyl monomer with 100 parts by weight of the binder resin.

 [0068] The colored resin particles obtained by the pulverization method obtained as described above are formed into core-shell structured colored resin particles by the same method as the colored resin particles obtained by the above-mentioned polymerization method, such as in situ polymerization. Monkey.

[0069] The toner of the present invention may be used as a toner by using colored resin particles as they are or by using colored resin particles and carrier particles (ferrite, iron powder, etc.). In order to adjust the properties, etc., use a high-speed stirrer (for example, Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.) etc.) to mix colored rosin particles and external additives to make a one-component toner. ,Also Preferably, the colored resin particles, the external additive, and the carrier particles are mixed to obtain a two-component toner.

 [0070] As external additives, inorganic fine particles such as silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, calcium phosphate, and sodium cerium; polymethyl methacrylate resin, silicone Examples thereof include organic fine particles such as rosin and melamine rosin. Of these, silica that is preferred for inorganic fine particles and silica that is more preferred for titanium oxide are more preferred.

 The addition amount of the external additive is usually 0.1 to 6 parts by weight, preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the colored resin particles. It is preferable to use two or more kinds of fine particles in combination as an external additive.

 The volume average particle diameter (Dv) of the toner is preferably 3 to 15 μm, and more preferably 4 to 12 m. If the Dv force is less than these ranges, the fluidity of the toner may deteriorate, transferability may deteriorate, blurring may occur, and the image density may decrease. May decrease.

 [0072] It represents the particle size distribution of the toner of the present invention. It (Dv / Dp) force S of volume average particle size (Dv) and number average particle size (Dp), preferably 1.00 to L30 And more preferably ί 1.00-: L20. If DvZDp exceeds these ranges, blurring may occur, and transferability, image density, and resolution may decrease. Dv and Dp can be measured using, for example, a particle size measuring device (Beckman Coulter, trade name: Multisizer).

 [0073] (Second invention)

 In the toner of the present invention, since the release agent is an (3) aliphatic hydrocarbon polymer having the following characteristics (1) and (2): It exhibits functions similar to those of low-soft spot materials used as mold release agents, but unlike conventional mold release agents, it improves low-temperature fixability and improves storage stability and print durability, especially at high temperatures. Improvement in printing durability after storage can be achieved.

 (1) The penetration at 25 ° C (JIS K2235-1991) is 3 or less.

(2) The solubility in toluene at 25 ° C is 5 to 60% by weight. (3) An aliphatic hydrocarbon polymer having the characteristics (1) and (2).

 From the viewpoint of penetration, the peak top molecular weight of the aliphatic hydrocarbon polymer is preferably 5,000 or more, more preferably 10,000 or more. When the molecular weight is less than the above range, the obtained toner is liable to have poor printing durability after high-temperature storage.

[0074] In the present invention, the penetration at 25 ° C for specifying the aliphatic hydrocarbon polymer is

This is a numerical value measured at a sample temperature of 25 ° C in accordance with the petroleum wax penetration test method stipulated in JIS K2235-1991. In the present invention, the penetration value is expressed to one decimal place.

 The outline of the test method is as follows.

 <Outline of penetration test method>

 The sample is heated and melted, placed in a sample container, allowed to cool, then kept within 25 ± 0.1 ° C in a constant temperature water bath, and a specified needle with a total mass of lOOg enters the sample vertically for 5 seconds. Let The penetration of the sample is expressed as a numerical value (anonymous number) obtained by measuring the depth of penetration of the needle up to 0.1 mm and multiplying this by 10 times.

 [0075] The aliphatic hydrocarbon polymer used in the toner of the present invention has a penetration of 3 or less at 25 ° C, preferably 2 or less, more preferably 1 or less.

 When the penetration of the aliphatic hydrocarbon polymer at 25 ° C is within the above range, both low temperature fixation and durability after high temperature storage are good.

 On the other hand, when the penetration is larger than the above range, the printing durability after high temperature storage deteriorates.

 [0076] In the present invention, the solubility in toluene at 25 ° C for specifying the aliphatic hydrocarbon polymer represents the content of the solute at a saturated concentration in toluene at 25 ° C. In the present invention, it is expressed as a ratio of the weight of the solute to the weight of the entire solution (that is, the sum of the solvent and the solute).

 The outline of the method for testing the solubility of the release agent is as follows.

 <Outline of solubility test method for release agent>

After heating toluene to 30 ° C. or higher, a release agent was added with stirring until it could not be completely dissolved to obtain a saturated release agent solution. The resulting saturated solution is then cooled to 25 ° C (room temperature). Then, the undissolved release agent was filtered through a filter to obtain a saturated solution. Toluene was removed from the obtained saturated solution, and the weight of the release agent as a solute was measured, and the concentration (weight%) of the saturated solution was calculated to obtain a solubility value.

 In the present invention, the solubility of the aliphatic hydrocarbon polymer in toluene at 25 ° C. is 5 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the solubility of an aliphatic hydrocarbon polymer at 25 ° C is within the above range, the aliphatic hydrocarbon polymer is subjected to a polymerization step performed in a process for producing colored resin particles such as a suspension polymerization method. Since the compatibility between the aromatic hydrocarbon polymer and the other raw material is high, a sufficient amount of the aliphatic hydrocarbon polymer can be added to the raw material.

 On the other hand, when the solubility is smaller than the above range, if the addition amount of the aliphatic hydrocarbon polymer is not limited to a small amount in the polymerization step, aliphatic hydrocarbon heavy in the raw material is used. The coalescence distribution is non-uniform. If the process temperature of the polymerization reaction is increased, a sufficient amount of an aliphatic hydrocarbon polymer having low solubility can be added.

There are problems such as difficulty in controlling the polymerization reaction and the inability to properly adjust the molecular weight of the binder resin.

 In addition, when this solubility is larger than the above range, no particular problem occurs, but from the viewpoint of compatibility between the aliphatic hydrocarbon polymer and other raw materials, solubility beyond the above range is particularly necessary. Not.

 [0078] In the second invention, the peak top molecular weight Mp of the α-olefin polymer is 15,000 to: L 10,000 force preferred <20,000 to 100,000 force ^ more preferred! / ヽ.

 In the second invention, the detailed description of the aliphatic hydrocarbon polymer other than those described above is the same as that of the first invention, and will be omitted.

 The other additives and the manufacturing method of the toner according to the second invention are the same as those described for the toner according to the first invention, and are therefore omitted.

[0079] (Third invention)

Further, in the toner of the present invention, the release agent is (3) an aliphatic hydrocarbon polymer having the following characteristics (1) and (2). In terms of Conventionally, it exhibits a function similar to a low softening point substance used as a release agent for toners, but unlike conventional release agents, it has improved low-temperature fixability and improved storage stability and printing durability. In particular, it is possible to improve the printing durability after high-temperature storage.

 (1) Melting point (TmD) is 70 ° C or less.

 (2) The penetration at 25 ° C (JIS K2235-1991) is 3 or less.

 (3) An aliphatic hydrocarbon polymer having the characteristics (1) and (2).

 [0080] In the third invention, the melting point (TmD) of the release agent is 70 ° C or lower, preferably 40 ° C or higher and lower than 70 ° C, more preferably 45 ° C or higher and lower than 65 ° C. Further preferred. The above range is preferable because both the storage stability and low-temperature fixability of the obtained toner are excellent.

 The aliphatic hydrocarbon polymer used in the toner of the third invention has a penetration of 3 or less at 25 ° C., preferably 2 or less, more preferably 1 or less. When the penetration is larger than the above range, storage stability and printing durability are deteriorated. The penetration is measured in the same manner as in the second invention.

 In the third invention, the peak top molecular weight (Mp) of the release agent is preferably 10,000,000-100,000, more preferably 20,000-90,000, and the weight average molecular weight of the release agent. Mw ί, 10, 000-100,000 force is preferred, 20,000-90,000 force is more preferred! / ヽ.

 In the third invention, the detailed description of the aliphatic hydrocarbon polymer other than those described above is the same as that of the first invention, and will be omitted.

 The other additives and the manufacturing method of the toner according to the third invention are the same as those described for the toner according to the first invention, and are therefore omitted.

[0081] (Fourth Invention)

 Sarakuko is a release agent in the toner of the present invention.

 (1) an aliphatic hydrocarbon polymer having a peak top molecular weight of 10,000 or more and a melting point of 70 ° C or less; and

 (2) Low molecular weight wax with a peak top molecular weight of 5,000 or less

 As a result, it is possible to improve the storage stability and low-temperature fixability of the toner, as well as offset resistance and printing durability.

[0082] In the fourth invention, the peak top molecular weight (Mp) of the aliphatic hydrocarbon polymer is more Preferred <is 10, 000 to 100,000, and more preferred <is 20,000 to 90,000

. If the peak top molecular weight of the aliphatic hydrocarbon polymer is within the above range, the balance between the storage stability of the toner and the low-temperature fixability is good, and the printing durability is excellent.

 The melting point of the aliphatic hydrocarbon polymer is 70 ° C. or lower, preferably 40 ° C. or higher and lower than 70 ° C., more preferably 45 ° C. or higher and lower than 65 ° C. When the melting point of the aliphatic hydrocarbon polymer is in the above range, the obtained toner is preferable because it has excellent storability and low-temperature fixability and excellent printing durability.

 In the fourth aspect of the invention, the detailed description of the aliphatic hydrocarbon polymer other than those described above is the same as that of the first aspect of the invention.

[0083] In the fourth invention, a low molecular weight wax having a peak top molecular weight of 5,000 or less is used in combination with the above-mentioned specific aliphatic hydrocarbon polymer as a release agent. By using this low molecular weight wax, the effect of improving the offset resistance can be obtained.

 Low molecular weight waxes include, for example, animal and plant waxes such as candelilla, carnauba, rice, wood wax, and jojoba; natural waxes such as paraffin, microcrystalline, and petrolatum, such as petroleum wax, and modified waxes thereof; and low molecular weight Polyolefin wax such as polyethylene, low molecular weight polypropylene, and low molecular weight polybutylene; Fischer-Tropsch wax; fatty acid ester of linear saturated monohydric alcohol, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of diglycerin, Synthetic waxes such as ester waxes such as fatty acid esters of dipentaerythritol and fatty acid esters of polyglycerol; ester amide waxes; ketone waxes; substituted urea compounds; And the like. Of these, ester wax is preferred!

 Among ester waxes, compounds with a branching number of 3 or more are preferred from the viewpoint of solubility in monomers during toner synthesis. Specifically, glycerol tristearate, glycerol tribehenate, pentaerythritol tetrapalmitate are preferred. Pentaerythritol tetrastearate, diglycerin tetrapalmitate, diglycerin tetrastearate, dipentaerythritol hexamyristate, dipentaerythritol hexapalmitate, and the like.

[0084] The peak top molecular weight (Mp) of the low molecular weight wax used in combination with the aliphatic hydrocarbon polymer is The preferred range is 500 to 5,000, and the more preferred range is 1,000 to 4,500. The method for measuring the peak top molecular weight is the same as that for the aliphatic hydrocarbon polymer.

 The melting point of the low molecular weight wax is preferably 50 to 100 ° C., more preferably 60 to 90 ° C., and the aliphatic hydrocarbon polymer preferably has a melting point higher than that of the aliphatic hydrocarbon polymer. The temperature difference from the melting point is preferably 50 ° C or lower, more preferably 30 ° C or lower, and even more preferably 20 ° C or lower. When the melting point of the low molecular weight wax is within the above range, the toner obtained is preferable because it has excellent storage stability and low-temperature fixability.

[0085] In the fourth invention, the content of the release agent is preferably 4 to 60 parts by weight, more preferably 6 to 50 parts by weight, and still more preferably 100 parts by weight of the binder resin. Is 8-40 parts by weight. Of the release agents, the ratio of the content of the aliphatic hydrocarbon polymer to the low molecular weight wax (the content of the aliphatic hydrocarbon polymer Z the content of the low molecular weight wax) is 98/2 to 25 / 75 power S girls like 96/4 ~ 50/50 power girls like 94/6 ~ 55/45 power S more preferable. When the content of the release agent is within this range, the effect of the specific release agent in the present application can be sufficiently obtained.

 The other additives and the manufacturing method of the toner according to the fourth invention are the same as those described for the toner according to the first invention, and therefore will be omitted.

 Example

 [0086] The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.

<Example Series 1>

 The test methods performed in this example are as follows.

 (1) Measurement of thermal properties of wax by differential scanning calorimetry (DSC)

 Thermal characteristics such as the melting point of the wax were measured using a differential scanning calorimeter (trade name: RDC-220, manufactured by Seiko Instruments Inc.). A DSC curve was obtained by weighing 6-8 mg of wax in the sample holder and measuring the temperature from -20 ° C to 100 ° C in 10 ° CZ minutes. From this, the melting point (TmD) and the half width of the peak were obtained.

In Table 1-1, waxes with two melting points (TmD) have two peaks in the DSC curve. Also wax with multiple peaks When the peaks are separated, the full width at half maximum of each peak is the sum of the full widths at half maximum of each peak. It was described in 1-1.

[0088] (2) Toner particle size

 Volume average particle diameter Dv of toner and ratio of volume average particle diameter Dv to number average particle diameter Dp DvZ The particle size distribution represented by Dp is a particle size measuring machine (Beckman Coulter, trade name: Multisizer) Measure according to II). Measurement conditions were as follows: aperture diameter = 100 m, medium = Isoton II, concentration = 10%, number of measured particles = 100,000.

 Specifically, 5 to 20 mg of a toner sample is taken in a beaker, and a surfactant, preferably alkylbenzenesulfonic acid 0.1 to 1 ml is added. Add 0.5 to 2 ml of Isoton II to the beaker, moisten the toner, and then add 10 to 30 ml of Isoton II, and disperse with an ultrasonic disperser for 1 to 3 minutes. Measurement was performed with a measuring instrument.

[0089] (3) Storage stability of toner

 10 g of toner was put in a sealable container (made of polyethylene, capacity: 100 ml), sealed, and then submerged in a constant temperature water bath maintained at a temperature of 55 ° C. After 15 hours, the container was taken out from the thermostatic water bath, and the toner in the container was placed on a 42 mesh sieve. At this time, in order not to destroy the toner aggregation structure in the container, the toner should be gently taken out from the container and carefully transferred to a sieve. The sieve on which the toner was placed was vibrated for 30 seconds under the conditions of an amplitude of lmm using the powder measuring instrument (trade name: PowderTester, manufactured by Hosokawa Micron Corporation), and the weight of the toner remaining on the sieve was measured. The weight of the coagulated toner was used. The ratio (% by weight) of the weight of the aggregated toner to the weight of the toner initially placed in the container was calculated. Each sample was measured three times, and the average value was used as an index of storage stability.

[0090] (4) Volume resistivity of toner

Toner 3.9g was pressure molded using a molding machine (product name: BRM-30 type, manufactured by Maekawa Tester Manufacturing Co., Ltd.) under a pressure of 100kgfZcm ² for 1 minute, and the disk shape was 5cm in diameter and 2mm in thickness. A sample for measurement was obtained. The obtained sample for measurement was measured with a dielectric loss measuring device (trade name: TRS-10, manufactured by Ando Electric Co., Ltd.) under the conditions of a temperature of 30 ° C. and a frequency of 1 kHz to obtain a volume resistivity. [0091] (5) Minimum fixing temperature of toner (low temperature fixing property)

 A fixing test was conducted using a commercially available non-magnetic one-component development printer (A4 22 sheets, Z printing speed) with a printer modified to change the temperature of the fixing roll. In the fixing test, black solid (printing density 100%) is printed, the temperature of the fixing roll of the modified printer is changed, the toner fixing rate at each temperature is measured, and the relationship between the constant temperature fixing rate is shown. I asked for it.

 The fixing rate was calculated from the ratio of the image density before and after the tape was peeled off in the solid black area (printing density 100%). That is, if the image density before tape peeling is ID (front) and the image density after tape peeling is ID (back), the fixing ratio can be calculated by the following equation.

 Fixing rate (%) = (ID (back) / ID (front)) X 100

 Here, the tape peeling operation refers to attaching an adhesive tape (product name: Scotch Mending Tape 810-3-18) manufactured by Sumitomo 3EM to the measurement part of the test paper, pressing it with a constant pressure, and then attaching it. It is a series of operations to peel the adhesive tape in a direction along the paper at a constant speed. Further, the image density was measured using a reflection type image density measuring device (manufactured by Macbeth, trade name: RG914).

 In this fixing test, the lowest fixing roll temperature at which the fixing rate exceeds 80% was evaluated as the minimum fixing temperature of the toner.

[0092] (Production Example I 1) Wax I A

 (Catalyst production example)

 Production of (1, 2'-dimethylsilylene) (2, 1'-dimethylsilylene) bis (3 trimethylsilylmethylindulur) zirconium dichloride

 In a 200 ml Schlenk bottle under a nitrogen stream, add 2.5 g (7.2 mmol) of (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (indene) and 100 ml of ether. The mixture was cooled to 78 ° C., 9.0 ml (14.8 mmol) of n-butyllithium (n-BuLi) in hexane (concentration 1.6 mol / l) was added, and the mixture was returned to room temperature and stirred for 12 hours.

The obtained solution force was also distilled off, and the remaining solid was washed with 20 ml of hexane and dried under reduced pressure to obtain (1, 2, -dimethylsilylene) (2, 1, -dimethylsilylene) bis ( I Was obtained quantitatively as a white solid.

 Next, in a Schlenk bottle, the obtained lithium salt of (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (indene) (6.97 mmol) was dissolved in 50 ml of tetrahydrofuran (THF). Then, 2. 1 ml (14.2 mmol) of odomethyltrimethylsilane was slowly added dropwise at room temperature and stirred for 12 hours.

 After stirring, the solvent was distilled off and 50 ml of ether was added. Further, a saturated aqueous solution of sodium chloride and ammonium salt was added thereto, washed, the aqueous phase was separated, the organic phase was dried, the solvent was removed, and (1, 2, monodimethylsilylene) (2 , 1'-dimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5.9 mmol) was obtained (yield 84%).

[0093] The (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above (3, 04 g, 5.9 mmol) and ether (50 ml) were combined with nitrogen. Put in a Schlenk bottle under air flow, cool to -78 ° C, add 7.4 ml (l l. 8 mmol) of hexane solution (1.6 mol Z liter) of n-butyllithium (n-BuLi). After returning to room temperature, the mixture was stirred for 12 hours.

 The solvent was distilled off from the stirred solution, and the remaining solid was washed with 40 ml of hexane to obtain 3.06 g of an ether adduct of lithium salt.

 When 1H-NMR of this lithium salt ether-attached case was determined, the following results were obtained.

 1H-NMR (90MHz, THF— d8): δ 0.04 (s, — SiMe3, 18H), 0.48 (s,-Me2Si—, 12H), 1. 10 (t, — CH3, 6H), 2 59 (s, — CH2—, 4H), 3. 38 (q, -CH2-, 4H), 6. 2- 7. 7 (m, Ar— H, 8H)

[0094] Under nitrogen flow, 3.06 g of the lithium salt ether adduct obtained above was suspended in 50 ml of toluene, cooled to -78 ° C, and pre-cooled to -78 ° C here. 1. A suspension of 2 g (5. lmmol) in toluene (20 ml) was added dropwise, and the mixture was returned to room temperature and stirred for 6 hours.

After the solvent of the obtained solution was distilled off, the remaining solid was recrystallized from dichloromethane to obtain (1, 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindulur) zirconium. Obtained 0.9 g (l. 33 mmol) of yellow fine crystals of dichloride. ( (Yield 26%)

 The following results were obtained when 1H-NMR of the yellow microcrystals was determined.

 1H-NMR (90MHz, CDC13): δ 0.0 (s, —SiMe3—, 18H), 1.02, 1.12 (s, — Me3Si—, 12H), 2.51 (dd, CH2—, 4Η ), 7. 1— 7. 6 (m, Ar— Η, 8Η

)

 [0095] (alpha 1-year-old refin polymerization)

 Heat-dried 10-liter autoclave and α-olefin (made by Idemitsu Kosan Co., Ltd., trade name: “Linearene 2024” (mainly a mixture of α-olefin with carbon numbers 20, 22, and 24, and its composition Is less than C18: 4.2%, C20: 41.9%, C22: 36.2%, C24: 16.9%, C26: 0.8%;))) 3L, heptane 3L, and polymerization After the temperature was raised to 80 ° C, 15 mmol of triisobutylaluminum, (1, 2'-dimethylsilylene) (2, -dimethylsilylene) bis (3 trimethylsilylmethylindul) zirco obtained in the above catalyst production example -60 μmol of dichloride (toluene slurry [20 μmol / mL, 3 mL]), 240 μmol of dimethyla-ryutetrakispentafluorophenol (toluene slurry [20 μmol / mL, 12 mL]) In the meantime, hydrogen was introduced at 0.08 MPa and polymerized for 4 hours. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, and then heated and dried under reduced pressure to obtain 2.Okg of a higher α-olefin polymer, which was designated Wax IA. The obtained wax I—A had Mw = 48,000, Mw / Mn = 1.9, TmD = 52.0 ° C., and half-value width 8 ° C.

 [0096] (Production Example I 2) Wax I B

 (Monomer preparation)

 The a-olefin (product name: “Linearene 2 024” manufactured by Idemitsu Kosan Co., Ltd.) used in Production Example I 1 was distilled under reduced pressure (2 to 14 mmHg) at a distillation temperature of 140 to 230 ° C. Thus, α-olefin having a carbon number of C22: 63.5% and C24: 36.5% was obtained. The obtained hyolephine fraction was introduced into a heat-dried 5 liter Schlenk and dehydrated with dry nitrogen and active alumina for 8 hours.

 (α-year-old refin polymerization)

Dehydrated α-olefin fin fraction in a heat-dried 10 liter autoclave 5 After adding a liter and raising the polymerization temperature to 75 ° C, 12 mmol of triisobutylaluminum (1, 2, -dimethylsilylene) (2, 1, -dimethylsilylene) bis (3 Trimethylsilylmethylinduluryl) zirconium dichloride 25 μmol (toluene slurry [20 / z molZmL, 1. 25 mL]), dimethylaureum tetrakispentafluorophenolate 100 μmol (toluene slurry [20 μmol / mL, 5 mL]) was introduced, and 0.05 MPa of hydrogen was introduced, followed by polymerization for 4 hours.

 After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 1.7 kg of a higher α-olefin copolymer, which was designated as wax IB. The obtained wax IB had Mw = 53,000, Mw / Mn = l.9, TmD = 62.0 ° C, and half-value width 6 ° C.

 [0097] (Example I 1)

 81 parts of styrene and 19 parts of n-butyl acrylate as monobule monomers (Tg = 55 ° C of the copolymer obtained by copolymerizing these monomers), polymetatalic acid ester macromonomer as macromonomer (Product name: AA6, Tg = 94 ° C, manufactured by Toa Gosei Kagaku Kogyo Co., Ltd.) 0.3 part, 0.5 part of divinylbenzene as a crosslinkable monomer, 1.2 part of tudedecyl mercabtan as a molecular weight regulator, and As a black colorant, 7 parts of carbon black (trade name: # 25B, manufactured by Mitsubishi Chemical Co., Ltd.) was wet-ground using a media type disperser. In the mixture obtained by wet pulverization, charge control resin as a charge control agent (manufactured by Fujikura Kasei Co., Ltd., trade name: Fataribase Jihachi 207?) 10 parts were added, mixed and dissolved to obtain a polymerizable monomer composition.

 [0098] On the other hand, an aqueous solution in which 8.1 parts of sodium chloride magnesium was dissolved in 170 parts of ion-exchanged water and an aqueous solution in which 4.5 parts of sodium hydroxide sodium was dissolved in 50 parts of ion-exchanged water were gradually stirred. Upon addition, a magnesium hydroxide colloidal dispersion was prepared.

 [0099] On the other hand, 1 part of methyl methacrylate (Tg = 105 ° C of the resulting polymer) and 65 parts of water were finely dispersed in an ultrasonic emulsifier, and water for the polymerizable monomer for the shell was used. A dispersion was obtained.

[0100] The polymerizable monomer composition was added to the hydroxy-magnesium colloidal dispersion obtained above (amount of hydroxy-magnesium colloid: 3.3 parts), and the mixture was stirred and polymerized there. T-butyl peroxyisoptylate (manufactured by NOF Corporation, trade name: Perbutyl IB) 6 parts were added. The dispersion added with the polymerization initiator is dispersed with an in-line type emulsifying disperser (trade name: Ebara Milder MDN303V, manufactured by Ebara Seisakusho Co., Ltd.) at a rotation speed of 15, and the speed is OOOrpm. Polymerizable monomer composition Droplets were formed.

 [0101] The dispersion formed into droplets is put into a reactor, and the polymerization reaction is carried out by raising the temperature to 95 ° C! / ヽ, after the polymerization conversion rate reaches almost 100%, 2, 2'-azobis (2-methyl-N- (2-hydride mouth kichetil) -propionamide) (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator for shells in an aqueous dispersion of polymerizable monomer for shell : VA-086, water soluble) 0.1 part was dissolved and added to the reactor. Further, the polymerization was continued at 95 ° C. for 4 hours, and then the reaction was stopped by cooling with water to obtain an aqueous dispersion of core-shell type colored resin particles.

 [0102] While stirring the obtained aqueous dispersion of colored rosin particles, washing with an acid to which sulfuric acid is added until the pH is 4.5 or less (25 ° C, 10 minutes), filtration is performed. It was dehydrated and further dried to obtain dried colored rosin particles.

 [0103] 100 parts of dried colored resin particles 1 part of silica fine particles hydrophobized with cyclic silazane (number primary average particle size: 7 nm) and silica fine particles hydrophobized with amino-modified silicone oil ( Number average primary particle size: 35 nm) 1 part was added and mixed using a high-speed stirrer (trade name: Henschel mixer, manufactured by Mitsui Mining Co., Ltd.) to prepare a toner for developing a non-magnetic one-component electrostatic image. . The test results are shown in Table I2.

 [Example I 2]

 In Example 1, a toner for developing an electrostatic charge image was prepared in the same manner as in Example I 1 except that instead of wax I-A, wax I-B obtained in Production Example I-2 was used. did. The test results are shown in Table I2.

 [0105] (Comparative Example I 1)

 In Example 1-1, a commercially available wax IC (trade name: VYBER253, manufactured by Toyo Petrolite Co., Ltd.) was used instead of wax IA. A toner for developing an electrostatic charge image was prepared in the same manner as in Example 1 except that the monomer composition or a dispersion in which the droplets thereof were dispersed was heated and processed at 50 ° C. while being heated. The test results are shown in Table I2.

[0106] (Comparative Example I 2) In Example I-1, wax I-D (manufactured by Nippon Seiki Co., Ltd., trade name: WEISSEN-T-68) was used instead of wax I-A, and from the dissolution of the wax to the temperature rise during the polymerization, The toner for developing an electrostatic charge image was prepared in the same manner as in Example 1-1, except that the polymerizable monomer composition or the dispersion liquid in which the droplets thereof were dispersed was heated and maintained at 50 ° C. Prepared. The test results are shown in Table I2.

[0107] (Comparative Example I 3)

 In Example 1-1, a commercially available wax I-E (manufactured by NOF Corporation, trade name: WEP6) was used instead of the wax I-A, and the solubility of the wax was also polymerized until the temperature increased during the polymerization. A toner for developing an electrostatic charge image was prepared in the same manner as in Example 1-1, except that the monomer composition or the dispersion liquid in which the droplets were dispersed was kept at 50 ° C while being heated. did. The test results are shown in Table I2.

 [0108] The physical properties of wax IA and wax IB obtained in the above production examples used in Examples of the present invention, and commercially available wax I-C, wax I-D, and wax IE used in Comparative Examples are as follows. Table I 1 shows.

 [0109] [Table 1]

 Table 1-1

[0110] [Table 2] Table I— 2

 [0111] From the test results described in Table 1-2, the following can be understood.

 The toner of Comparative Example I 1 containing wax C, which has two melting points (TmD) defined as the temperature at the top of the peak in the DSC curve by the differential scanning calorimeter (DSC), was completely The minimum fixing temperature was insufficient for both high storage stability and low-temperature fixability.

 Similarly to the wax I-C, the toner of Comparative Example I-2 having two melting points (TmD) and having a peak half-value width exceeding 10 ° C and containing the wax I-D has a storage stability. The test showed that the toner was completely agglomerated and the minimum fixing temperature was higher than that of the toner of Comparative Example I 1 and both the storage stability and the low-temperature fixing property were insufficient.

 In addition, the toners of Comparative Examples 1 to 3 containing wax E, which is an ester wax, had good storage stability, but had a high minimum fixing temperature and insufficient low-temperature fixing properties. In contrast, the toners of the examples containing the specific higher α-olefin polymers defined in the present invention were good in both storage stability and low-temperature fixability.

[0112] <Example Series II>

 The test methods performed in this example are as follows.

 (1) Measurement of thermal properties of release agent by differential scanning calorimetry (DSC)

 In the same manner as in Example Series I, thermal characteristics such as the melting point of the release agent were measured.

[0113] (2) Penetration at 25 ° C

The penetration test was performed in accordance with JIS K2235—1991. As an instrument for measuring the penetration, an automatic penetration meter (trade name: RPM-101, manufactured by Kouaisha) was used. [0114] (3) Solubility of mold release agent at 25 ° C

 After heating 100 g of toluene in a 500 ml container to 40 ° C., a release agent was added with stirring until it could not be completely dissolved to obtain a saturated release agent solution. Thereafter, the obtained saturated solution was cooled to 25 ° C. (room temperature), and the undissolved release agent was filtered with a filter to obtain a saturated solution. Toluene was removed from the obtained saturated solution, and the weight of the release agent as a solute was measured, and the concentration (% by weight) of the saturated solution was calculated to obtain a solubility value.

[0115] (4) Molecular weight of release agent

 The molecular weight of the release agent was determined as a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

 Specifically, a GPC measuring device (manufactured by Waters, trade name: Alliance GPC 2000) was used as the measuring device. In addition, the solution to be injected was 240 μ 1 of 1,2,4-trichloro-benzene (containing 300 ppm of dibutylhydroxytoluene) having a concentration of 0.5 mgZml, and the column was a mixed polystyrene gel column (Tosohichi Corporation) Using a product name: GMHHR—H (S) ΗΤ), a column temperature of 145 ° C. and a flow rate of 1. OmlZmin were used for measurement. For detection, an infrared detector was used and a wavelength of 3.41 μm was used.

[0116] (5) Toner particle size

 Volume average particle diameter Dv of toner and ratio of volume average particle diameter Dv to number average particle diameter Dp DvZ The particle size distribution represented by Dp is a particle size measuring machine (Beckman Coulter, trade name: Multisizer) Measured according to i). Measurement conditions were as follows: aperture diameter = 100 m, medium = Isoton II, concentration = 10%, number of measured particles = 100,000.

 Specifically, 0.2 g of a toner sample was placed in a beaker, and an alkylbenzenesulfonic acid aqueous solution (Fuji Film Co., Ltd., trade name: Drywell) was added as a dispersant. Then, 2 ml of Isoton II was further added, and the toner was moistened. Then, 10 ml of Isoton II was added and dispersed for 1 minute with an ultrasonic disperser.

[6] (6) Volume resistivity of toner

 It measured by the method similar to Example series I, and obtained volume resistivity.

[0118] (7) Minimum toner fixing temperature (low-temperature fixability) Measurement and evaluation were performed in the same manner as in Example Series I.

[0119] (8) Storage stability of toner

 The measurement was performed in the same manner as in Example Series I.

[0120] (9) Printing durability

 Put the toner in a commercially available non-magnetic one-component development printer (printing speed: A4 size, 24 sheets, Z, 1 minute), and in the environment of 23 ° C and 50RH% (normal temperature and humidity), 5% print density from the beginning Continuous printing, solid printing (100% printing density) and white solid printing (0% printing density) at the 500th printing, with a reflective image density meter (made by Macbeth, product name: RD914) for solid printing The number of continuous prints can be maintained at a print density of 1.3 or higher, and with white solid printing, the image on the photoconductor after development measured with a whiteness meter (Nippon Denshoku) can maintain an image quality of 5% or less. The durability of the toner was evaluated.

 Specifically, the capri was measured as follows. Remove the toner on the photoconductor after development with an adhesive tape (Scotch Mending Tape 810-3-18, manufactured by Sumitomo 3EM) and affix it to new printing paper to reduce the whiteness B (%). On the other hand, the whiteness A (%) of the printing paper in which only the adhesive tape was pasted on the new printing paper was measured and calculated by the following formula.

 Capri (%) = Whiteness A Whiteness B

[0121] (10) Printing durability (after leaving at high temperature)

 400 g of toner is put in a toner cartridge, this cartridge is sealed with an aluminum bag, and then submerged in a constant temperature water bath maintained at a temperature of 50 ° C. After 5 days, the force cartridge was taken out of the thermostatic water bath, and thereafter the printing durability was tested in the same manner as in the above (9).

[0122] (Production Example II 1) Wax II A

 A higher α-olefin polymer was obtained in the same manner as the wax IA of Production Example I1, and was obtained as Lux II.

[0123] (Production Example II 2) Wax II B

 A higher α-olefin polymer was obtained in the same manner as in the wax IB of Production Example I1, and it was designated as Lux II.

[0124] (Production Example II 3) Wax II C A commercial pentaerythritol tetrastearate (manufactured by NOF Corporation, trade name: WEP6) is dissolved in toluene heated to 40 ° C to make a 20 wt% solution, and then cooled to 5 ° C. Erythritol tetrastearate was recrystallized. While maintaining the temperature at 5 ° C., the recrystallized component was filtered with filter paper, and the recrystallized component on the filter paper was vacuum-dried at 50 ° C. for 24 hours to obtain Wax C.

 [0125] Table II 1 shows the analysis results and properties of the waxes obtained in the production examples and various commercially available waxes.

[0126] [Table 3]

Table I I 1

(Example II 1)

 A toner was obtained in the same manner as in Example I1.

[0128] (Example II 2)

 Example Π-1 was the same as Example Π-1, except that wax 離 -Β obtained in Production Example Π-2 was used in place of wax Π-A as a release agent. A toner was obtained.

[0129] (Comparative Example II 1)

 In Example Π-1, a commercially available paraffin wax (manufactured by Nippon Seisaku Co., Ltd., product name: PW130) was used as a mold release agent in place of wax II A. From the dissolution of the mold release agent to polymerization, A toner was obtained in the same manner as in Example V-1, except that the monomer composition, the dispersant, and the mixture thereof were heated to 50 ° C. or higher.

[0130] (Comparative Example II 2)

 In Example Π-1, in place of wax Π-A as a release agent, a commercially available ester box (manufactured by NOF Corporation, trade name: WEP6) was used, from dissolution of the release agent to polymerization. A toner was obtained in the same manner as in Example II-1, except that the monomer composition, the dispersant, and the mixture thereof were heated to 40 ° C. or higher.

 (Comparative example Π— 3)

 Example Π-1 was the same as Example 離 -1, except that wax Π-C obtained in Production Example Π-3 was used in place of wax Π-A as a release agent. A toner was obtained.

[0131] The results of Examples and Comparative Examples are shown in Table II2.

[0132] [Table 4]

Table II 1 2

In Examples II-1 and Π-2, as a mold release agent, a-olefin polymer wax (wax Π-A, wax Π) satisfying the conditions specified in the present invention in terms of penetration and solubility in toluene. — Using (ii), almost no blocking occurred in the storability test when the minimum fixing temperature was low.In addition, either the general printing durability test or the printing durability test after being left at high temperature The number of prints that produced capri was also very strong. In particular, the number of printed sheets in the print durability test after standing at high temperature was characteristic in that it was not much different from the number of printed sheets in which the capri was generated in a general print durability test.

 In contrast, in Comparative Example 例 -1, when the commercially available paraffin wax was used, the minimum fixing temperature of the toner was the same as in Examples Π-1 and Π-2. In the general printing durability test and the printing durability test after being left at a high temperature, the number of printed sheets was very small. In particular, the number of prints that generated capri in the print durability test after being left at high temperature was 5,000, and the start force for continuous printing occurred very early.

 In Comparative Example Π-2, when the commercially available ester wax WEP6 was used, the minimum fixing temperature of the toner was higher than that of Examples Π-1 and Π-2. Therefore, the occurrence of blocking in the storage test was almost strong. However, in both the general printing durability test and the printing durability test after being left at a high temperature, the number of prints where the capri was generated was smaller than those in Examples V-1 and V-2. In Comparative Example Π-2, although not as much as in Comparative Example Π-1, compared to the results of a general printing durability test, the number of printed sheets that causes a capri in the printing durability test after being left at high temperature, A tendency to become smaller was observed.

In Comparative Example Π-3, when the wax Π-C obtained by purifying the ester wax used in Comparative Example II 2 was used, the minimum fixing temperature was the same. Little force was generated (1%). In addition, because it is a refined wax, the number of prints that generate capri is greater in both the general print durability test and the print durability test after being left at high temperature compared to Comparative Example Π-2. It was. However, it was still inferior to the results of the printing durability test of Examples Π-1 and Π-2. In particular, comparative example Π— 3 Even in this case, compared with the result of the general printing durability test, there was a tendency that the number of printed sheets in which the capri was generated in the printing durability test after being left at a high temperature tended to be small. In this respect, Example II 1 and V-2 were remarkably excellent in printing durability after being left at high temperature.

 <Example Series III>

 The test methods performed in this example are as follows.

 (1) Measurement of thermal properties of release agent by differential scanning calorimetry (DSC)

 In the same manner as in Example Series I, the thermal characteristics such as the melting point of the release agent were measured to obtain a DSC curve. From this, the peak of the DSC curve was identified as the melting point (TmD).

[0135] (2) Degree of penetration

 The penetration of the release agent was measured in the same manner as in Example Series II.

[0136] (3) Molecular weight of release agent

 Example Series The molecular weight of the release agent was determined in the same manner as in Sakai.

[0137] (4) Toner particle size

 The volume average particle size Dv and the particle size distribution DvZDp of the toner were measured by a particle size measuring device (Beckman Co., Ltd., trade name: Multisizer 1). The measurement with this multisizer was carried out under the conditions of an aperture diameter of 100 m, a medium of Isoton II, a concentration of 10%, and the number of measured particles: 100,000.

 Specifically, 0.2 g of a toner sample was placed in a beaker, and an alkylbenzenesulfonic acid aqueous solution (Fuji Film Co., Ltd., trade name: Drywell) was added as a dispersant. Then, 2 ml of Isoton II was further added, and the toner was moistened. Then, 10 ml of Isoton II was added and dispersed for 1 minute with an ultrasonic disperser.

[0138] (5) Toner volume resistivity

 Volume resistivity was obtained in the same manner as in Example Series I.

[0139] (6) Minimum toner fixing temperature (low-temperature fixability)

 Measurement and evaluation were performed in the same manner as in Example Series I.

[0140] (7) Storage stability of toner

The measurement was performed in the same manner as in Example Series I. [0141] (8) Printing durability

 Using a commercially available non-magnetic one-component development type printer (printing speed: A4 size, 24 sheets, Z), toner was put in the developing device. After standing for 24 hours in a room temperature and normal humidity (NZN) environment at a temperature of 23 ° C and a humidity of 50% RH, continuous printing was performed up to 17,000 sheets at 1% printing density in the same environment. The solid print (print density 100%) was printed every 1,000 sheets, and the print density of the solid print portion was measured with a reflection type image density meter (trade name: RD914, manufactured by Macbeth). After that, solid white printing (printing density 0%) is performed, the printer is stopped in the middle of white solid printing, and the toner on the non-image area on the developed photoconductor is adhesive tape (Sumitomo 3 Product, product name: Scotch Mending Tape 810-3-18), peeled off and pasted on printing paper. Next, the whiteness B (%) of the printing paper with the adhesive tape attached is measured with a whiteness meter (manufactured by Nippon Denshoku), and in the same way, only the unused adhesive tape is attached to the printing paper. The whiteness A (%) was measured, and the difference in whiteness (B—A) was defined as the capri value (%). Smaller values indicate better capri and better. The number of continuous prints that can maintain image quality with a print density of 1.3 or more and a capri value of 5% or less was examined.

[0142] (Production Example III 1) Wax III A

 A higher α-olefin polymer was obtained in the same manner as in the wax I A of Production Example I 1 to give a glass ΠΙ—Α.

[Production Example III 2] Wax III B

 A higher α-olefin polymer was obtained in the same manner as the wax IB of Production Example I 1 to obtain Lux III-Β.

[0144] (Example ΠΙ— 1)

 In the same manner as in Example I1, a non-magnetic one-component electrostatic image developing toner was prepared. The test results are shown in Table IV-1.

[0145] (Example ΠΙ— 2)

Example ΠΙ— 1! /, Wax III— Static electricity was charged in the same manner as Example III-1 except that wax III-B obtained in Production Example III-2 was used instead of Α. An image developing toner was prepared. The test results are shown in Table III-1. [0146] (Comparative Example ΠΙ— 1)

 Example ΠΙ-1! /, And wax III—commercially available in place of A !, Ru Wax ΠΙ-C (Nippon Seiki Co., Ltd., trade name: PW130) In the same manner as in Example 1, except that the polymerizable monomer composition or the dispersion liquid in which the droplets were dispersed was kept at 50 ° C. while being heated until the temperature was raised during the polymerization. A toner for developing an electrostatic image was prepared. The test results are shown in Table IV-1.

 [0147] (Comparative Example III 2)

 Example ΠΙ-1! /, And wax III—commercially available instead of A !, Ru Wax D-D (Nippon Yushi Co., Ltd., trade name: WEP—4) is used, and the dissolving power of the wax is also polymerized. In the same manner as in Example III-1, except that the polymerizable monomer composition or the dispersion liquid in which the droplets were dispersed was kept at 40 ° C. while being heated until the temperature was raised. A toner for developing an electrostatic image was prepared. The test results are shown in Table III-1.

 [0148] Wax III-A and Wax III obtained in the above production examples used in Examples of the present invention

 B, and the physical properties of commercially available wax III C and wax III D used in Comparative Examples are shown in Table III 1 below.

[0149] [Table 5]

(Summary of results)

 The test results shown in Table m-1 indicate the following.

Wax III, which is a paraffin wax whose penetration is greater than the prescribed range of the present invention III In the toner of Comparative Example m-i contained, the minimum fixing temperature was the same as in the examples, and the low-temperature fixability was good, but the toner blocked due to the storage stability test, and also according to the durability test. The number of printed sheets was as low as 10,000 and the storage stability and printing durability were poor.

 In addition, although the toner of Comparative Example in-2 containing wax m-D, which is an ester wax having a high melting point and a high penetration, is better than the prescribed range of the present invention, the storage stability was good. The minimum fixing temperature is high, and the number of printed sheets in the durability test is as low as 12,000. The low-temperature fixing property and the printing durability are inferior!

 On the other hand, in the toners of the examples containing the aliphatic hydrocarbon polymer having a specific range of melting point and a specific range of penetration as defined in the present invention, storage stability, low-temperature fixability, In addition, the deviation in printing durability was also good.

 [0151] <Example Series IV>

 The test methods performed in this example are as follows.

 (1) Measurement of thermal properties of release agent by differential scanning calorimetry (DSC)

 In the same manner as in Example Series I, the thermal characteristics such as the melting point of the release agent were measured to obtain a DSC curve. From this, the peak of the DSC curve was identified as the melting point (TmD).

[0152] (2) Peak top molecular weight of release agent

 Example Series The peak top molecular weight of the mold release agent was determined by the same method as that for Sakai.

[0153] (3) Toner particle size

 Example series Measurement was carried out in the same manner as in Sakai.

[0154] (4) Toner preservability

 The measurement was performed in the same manner as in Example Series I.

[0155] (5) Toner volume resistivity

 Volume resistivity was obtained in the same manner as in Example Series I.

[0156] (6) Minimum toner fixing temperature (low temperature fixability)

A fixing test was conducted using a commercially available non-magnetic one-component development printer (printing speed: A4 size, 28 sheets, Z minutes) with a printer modified to change the temperature of the fixing roll. The fixing test is to print a solid black (print density 100%) The toner fixing rate at each temperature was measured by changing the temperature of the toner, and the relationship between the constant temperature fixing rate was determined.

 The fixing rate was calculated from the ratio of the image density before and after the tape was peeled off in the solid black area (printing density 100%). That is, if the image density before tape peeling is ID (front) and the image density after tape peeling is ID (back), the fixing ratio can be calculated by the following equation.

 Fixing rate (%) = (ID (back) / ID (front)) X 100

 Here, the tape peeling operation refers to attaching an adhesive tape (product name: Scotch Mending Tape 810-3-18) manufactured by Sumitomo 3EM to the measurement part of the test paper, pressing it with a constant pressure, and then attaching it. It is a series of operations to peel the adhesive tape in a direction along the paper at a constant speed. The image density was measured using a reflection type image density meter (manufactured by Macbeth, trade name: RD914).

 In this fixing test, the minimum fixing roll temperature with a fixing rate exceeding 80% is reduced.

 The fixing temperature was evaluated.

 [0157] (7) Toner offset resistance

 A commercially available non-magnetic one-component development printer (printing speed: A4 size, 14 sheets, Z) was used so that the temperature of the fixing roll could be changed. In the offset resistance test, the temperature of the fixing roll of this modified printer was changed from 150 ° C to 220 ° C in increments of 10 ° C, and the black solid (print density 100%) and white solid (print density 0%) portions. A print pattern having a print was printed, and the white solid portion on the paper was observed at each temperature, and the presence or absence of an offset was visually confirmed. It was evaluated as X when the temperature at which high temperature offset occurred was less than 200 ° C, △ when 200 ° C to 220 ° C, and ◯ when 220 ° C or higher.

 [0158] (8) Printing durability

 Example series Measurement was carried out in the same manner as in Sakai.

 [0159] (Production Example IV— 1) Wax IV— A

 (Catalyst production example)

(1, 2'-dimethylsilylene) (2, 1'-dimethylsilylene) bis (3-trimethylsilylmethyl) Ruindur) Zirconium dichloride production

 In a 200 ml Schlenk bottle under a nitrogen stream, add 2.5 g (7.2 mmol) of (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (indene) and 100 ml of ether. The mixture was cooled to 78 ° C., 9.0 ml (14.8 mmol) of n-butyllithium (n-BuLi) in hexane (concentration 1.6 mol / l) was added, and the mixture was returned to room temperature and stirred for 12 hours.

 The obtained solution force was also distilled off, and the remaining solid was washed with 20 ml of hexane and dried under reduced pressure to obtain (1, 2, -dimethylsilylene) (2, 1, -dimethylsilylene) bis ( Inden) was obtained quantitatively as a white solid.

[0160] Next, in a Schlenk bottle, the lithium salt (6.97 mmol) of (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (indene) obtained was added to 50 ml of tetrahydrofuran (THF). Then, 2. 1 ml (14.2 mmol) of odomethyltrimethylsilane was slowly added dropwise at room temperature and stirred for 12 hours.

 After stirring, the solvent was distilled off and 50 ml of ether was added. Further, a saturated salt / ammonium aqueous solution was added thereto, washed, the aqueous phase was separated, the organic phase was dried, the solvent was removed, and (1, 2'-dimethylsilylene) (2, — Dimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5.9 mmol) was obtained (yield 84%).

[0161] The above-obtained (1, 2, 1-dimethylsilylene) (2, 1, 1-dimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5.9 mmol) and 50 ml of ether were mixed with nitrogen. Put in a Schlenk bottle under air flow, cool to -78 ° C, add hexane solution of n-butyllithium (n-BuLi) (1.6 molZD, 7.4 ml (l l. 8 mmol), The solvent was distilled off from the stirred solution, and the remaining solid was washed with 40 ml of hexane to obtain 3.06 g of an ether adduct of a lithium salt.

 When the 1H-NMR of the ether adduct of this lithium salt was measured, the following results were obtained.

1H-NMR (90MHz, THF— d8): δ 0.04 (s, — SiMe3, 18H), 0.48 (s,-Me2Si—, 12H), 1. 10 (t, — CH3, 6H), 2 59 (s, — CH2—, 4H), 3. 38 (q, -CH2-, 4H), 6. 2- 7. 7 (m, Ar— H, 8H) [0162] Lithium salt ether adduct 3.06 g obtained above was suspended in 50 ml of toluene in a nitrogen stream, cooled to -78 ° C, and pre-cooled to -78 ° C here. 1. A suspension of 2 g (5. Immol) in toluene (20 ml) was added dropwise, and the mixture was returned to room temperature and stirred for 6 hours.

 After the solvent of the obtained solution was distilled off, the remaining solid was recrystallized from dichloromethane to obtain (1, 2'-dimethylsilylene) (2, 1'-dimethylsilylene) bis (3-trimethylsilylmethylindulur) zirconium. This gave 0.9 g (l. 33 mmol) of yellow microcrystals of dichloride (yield 26%).

 When the 1H-NMR of this yellow microcrystal was measured, the following result was obtained.

 1H-NMR (90MHz, CDC13): δ 0.0 (s, — SiMe3—, 18H), 1.02—1.12 (s, — Me3Si—, 12H), 2.51 (dd, — CH2—, 4Η), 7. 1— 7. 6 (m, Ar— Η, 8Η

)

 [0163] (Monomer preparation)

 a-olefin (Product name: Linearlen 2024, manufactured by Idemitsu Kosan Co., Ltd.) was distilled under reduced pressure (2-14m mHg) at a distillation temperature of 140-230 ° C, and the composition was C22: 63.5% C24: 36. A 5% ex-olefin fraction was obtained. The obtained a-olefin fraction was introduced into a heat-dried 5 liter Schlenk bottle and dehydrated with dry nitrogen and activated alumina for 8 hours.

 [0164] (α-year-old refin polymerization)

 In a heat-dried 10 liter autoclave, 5 liters of dehydrated α-olefin was added and heated to a polymerization temperature of 75 ° C. Then, 12 mmol of triisobutylaluminum was obtained in the above catalyst production example (1 , 2, -dimethylsilylene) (2,1, -dimethylsilylene) bis (3-trimethylsilylmethylindul) zirconium dichloride 25 μmol (toluene slurry (20 / ζπιο1 / πι] ^, 1. 25 mL)), and dimethylaurly -Mutumakikis pentafluorophenol borate 100 μmol (toluene slurry (20 μmol / mL, 5 mL)) was charged, hydrogen 0.05MPa was introduced, and the polymerization temperature was maintained for 4 hours. I did it.

After completion of the polymerization reaction, the obtained reaction product is precipitated with acetone, and then heated and reduced in pressure. Then, the solvent was distilled off and dried to obtain 1.7 kg of α-olefin copolymer, which was designated as wax IV-A.

 [0165] (Example IV— 1)

 78 parts of styrene and 22 parts of n-butyl acrylate as monobule monomers (Tg = 50 ° C of the copolymer obtained by copolymerizing these monomers), polymetatalic acid ester macromonomer as macromonomer (Product name: AA6, Tg = 94 ° C, manufactured by Toa Gosei Kagaku Kogyo Co., Ltd.) 0.3 parts, 0.7 parts of divinylbenzene as a crosslinkable monomer, 1.85 parts of tudedecyl mercabtan as a molecular weight regulator, and 7 parts of carbon black (trade name: # 25B, manufactured by Mitsubishi Chemical Co., Ltd.) was black pulverized as a black colorant using a media type wet pulverizer. In the mixture obtained by wet pulverization, 1 part of charge control resin (trade name: Ataribase FCA—207P, manufactured by Fujikura Kasei Co., Ltd.) as a charge control agent and wax IV—A (Production Example 1) as a release agent Aliphatic hydrocarbon polymer obtained in 1) and 2 parts of wax IV-B (manufactured by NOF Corporation, trade name: WEP6) are added, mixed and dissolved to obtain a polymerizable monomer composition. It was.

 [0166] On the other hand, an aqueous solution in which 8.6 parts of sodium chloride magnesium was dissolved in 170 parts of ion-exchanged water and an aqueous solution in which 4.8 parts of sodium hydroxide sodium were dissolved in 50 parts of ion-exchanged water were gradually stirred. Upon addition, a magnesium hydroxide colloidal dispersion was prepared.

 [0167] The polymerizable monomer composition was added to the hydroxy-magnesium colloidal dispersion obtained above (amount of hydroxy-magnesium colloid 3.5 parts), and the mixture was further stirred and polymerized there. As an initiator, 6 parts of t-butylperoxyisoptylate (manufactured by NOF Corporation, trade name: perbutyl IB) was added. The dispersion added with the polymerization initiator is dispersed with an in-line type emulsifying disperser (trade name: Ebara Milder MDN303V, manufactured by Ebara Seisakusho Co., Ltd.) at a rotation speed of 15 and OOOrpm !, a polymerizable monomer composition Droplets were formed.

[0168] The dispersion in which droplets are formed is put into a reactor, and the polymerization reaction is carried out by raising the temperature to 95 ° C! / ヽ, after the polymerization conversion rate reaches almost 100%, 1 part of methyl methacrylate (Tg = 105 ° C. of the resulting polymer) which is a polymerizable monomer was added to the reactor. Next, 2, 2, monoazobis (2-methyl N— (2-hydride kichetil) monopropionamide) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble) 0 1 part was dissolved in 10 parts of water and added to the reactor. Furthermore, the polymerization was continued at 95 ° C for 4 hours, and then cooled with water. The reaction was stopped to obtain an aqueous dispersion of colored resin particles having a core-shell structure.

 [0169] While stirring the aqueous dispersion of the obtained colored resin particles, washing with an acid to which sulfuric acid is added until the pH becomes 4.5 or less (25 ° C, 10 minutes), followed by filtration It was dehydrated and further dried to obtain dried colored rosin particles.

 [0170] 100 parts of dried colored resin particles 1 part of silica fine particles hydrophobized with cyclic silazane (number primary average particle size: 7 nm) and silica fine particles hydrophobized with amino-modified silicone oil ( Number average primary particle size: 35 nm) 1 part was added and mixed using a high-speed stirrer (trade name: Henschel mixer, manufactured by Mitsui Mining Co., Ltd.) to prepare a toner for developing a non-magnetic one-component electrostatic image. . The test results are shown in Table IV-2.

 [0171] (Example IV-2)

 In Example IV-1, 8 parts of wax IV-A and 6 parts of wax IV-A and wax IV-C instead of 2 parts of wax IV-B as a release agent (trade name: manufactured by NOF Corporation) W EP7) An electrostatic charge image developing toner was prepared in the same manner as in Example IV-1, except that 4 parts were used. The test results are shown in Table IV-2.

 [0172] (Example IV-3)

 In Example IV-2, the same method as Example IV-2, except that the amount of wax added as a release agent was changed to 18 parts for wax IV-A and 2 parts for wax IV-C, respectively. A toner for developing an electrostatic image was prepared. The test results are shown in Table IV-2.

 [0173] (Comparative Example IV— 1)

 In Example IV-1, the toner for developing an electrostatic charge image was prepared in the same manner as in Example IV-1, except that 10 parts of wax IV-A was not used as the mold release agent. Prepared. The test results are shown in Table IV-2.

 [0174] (Comparative Example IV-2)

 In Example IV-1, the toner for developing an electrostatic charge image was prepared in the same manner as in Example IV-1, except that 10 parts of wax IV-B was not used as the mold release agent. Prepared. The test results are shown in Table IV-2.

 [0175] (Comparative Example IV-3)

In Example IV-1, 8 parts of wax IV-A and wax IV-B were used as mold release agents. Instead of 2 parts, 8 parts of wax IV-B and 2 parts of wax IV-D (manufactured by Nippon Seiki Co., Ltd., product name: PW130) are used, from dissolution of the release agent to temperature rise during polymerization, A toner for developing an electrostatic charge image in the same manner as in Example IV-1, except that the polymerizable monomer composition or the dispersion liquid in which the droplets were dispersed was heated and processed at 50 ° C while being heated. Was prepared. The test results are shown in Table IV-2.

[0176] (Comparative Example IV-4)

 In Example IV-1, as a release agent, instead of wax IV-A 8 parts and wax IV-B 2 parts, wax IV-C 8 parts and wax IV-E (manufactured by Nippon Seiki Co., Ltd., product) Name: FTIOO) A toner for developing an electrostatic image was prepared in the same manner as in Example 1 except that it was processed using 2 parts. Wax IV-E was not dissolved in the monomer, but was finely pulverized and dispersed by a wet pulverization process using a media-type wet pulverizer. The test results are shown in Table IV-2.

 [0177] The wax IV-A obtained in the above-mentioned production example and used in the examples or comparative examples of the present invention, as well as commercially available wax IV-B, wax IV-C, wax IV-D, and wax IV. — Physical properties of E are shown in Table IV-1 below.

[0178] [Table 6]

Table I V— 1

 ヮ 'NOX IV-A ΨΜ IV Μ IV-C WAX 1 V-0 ヮ' NOX IV-E WAX TYPE a— † REFIN POLYMER 1 box

 (EP6) (WEP7) (PW130) (FT100)

(DSC measurement)

 Melting point (TmD) C ° C) 60 76 73 56 98

(GPC measurement)

Hi-ku Molecular weight (Mp) 38, 000 2,500 3,900 1,300 2,400

Table I V— 2

[0181] (Summary of results)

 The test results described in Table IV-2 show the following.

 The toner of Comparative Example IV-1 using only wax A was excellent in storage stability and low-temperature fixability, but inferior in offset resistance.

 In addition, the toner of Comparative Example IV-2 using only wax IV-B has a minimum fixing temperature higher than that of Comparative Example IV-1, and the printing durability tends to be slightly deteriorated. Both sexes were insufficient.

 Furthermore, the toner of Comparative Example I V-3, which uses wax IV-B and wax IV-D, which is a paraffin wax, was insufficient in all of the characteristics of storage stability, low-temperature fixability, and printing durability.

 In addition, the toner of Comparative Example IV-4, which uses Wax IV-C and Fischer-Tropsch wax IV-E in combination, has a minimum fixing temperature higher than that of Comparative Example IV-1, and the printing durability tends to be slightly worse. Both low-temperature fixability and printing durability were insufficient.

 In contrast, the toners of the examples using the specific aliphatic hydrocarbon polymer and low molecular weight wax specified in the present invention are excellent in offset resistance and have both storage stability, low-temperature fixability, and printing durability. It was good.

 Industrial applicability

[0182] The electrostatic image developing toner obtained by the present invention can be used as a developer in an electrophotographic image forming apparatus such as a facsimile, a copying machine, and a printer.

Claims

Claims [1] In a toner for developing an electrostatic charge image comprising colored resin particles containing a binder resin, a colorant, and a release agent, the release agent polymerizes an aliphatic hydrocarbon monomer. An electrostatic charge image developing toner, which is an aliphatic hydrocarbon polymer. [2] The toner for developing an electrostatic charge image according to [1], wherein the aliphatic hydrocarbon polymer has a melting point (TmD) of less than 80 ° C. [3] The release agent is

 (1) A DSC curve by a differential scanning calorimeter (DSC) has one melting point (TmD) defined as the temperature at the top of the peak, and

 (2) The full width at half maximum of the peak is within 12 ° C

 (3) It is an aliphatic hydrocarbon polymer

 The electrostatic charge image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner.

[4] The release agent is

 (1) Penetration at 25 ° C (JIS K2235-1991) force or less, and

 (2) Solubility in toluene at 25 ° C is 5-60% by weight

 (3) It is an aliphatic hydrocarbon polymer

 The electrostatic charge image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner.

5. The electrostatic image developing toner according to any one of claims 1 to 4, wherein the aliphatic hydrocarbon polymer has a melting point (TmD) of 40 ° C or higher and lower than 80 ° C. .

[6] The release agent is

 (1) Melting point (TmD) is 70 ° C or less, and

 (2) Needle penetration at 25 ° C (JIS K2235-1991) is 3 or less

 (3) It is an aliphatic hydrocarbon polymer

 The electrostatic charge image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner.

7. The toner for developing an electrostatic charge image according to claim 6, wherein the aliphatic hydrocarbon polymer has a weight average molecular weight of 10,000 or more and 100,000 or less.

[8] The aliphatic hydrocarbon polymer polymerizes an α-aged lefin monomer having 10 or more carbon atoms. The electrostatic image developing toner according to claim 1, which is a higher a-olefin polymer.

9. The electrostatic image developing toner according to claim 8, wherein the toner is a polymer that is polymerized in the presence of a meta-octene compound as a catalyst for the high-grade oc single-year-old refin polymer.

10. The electrostatic image developing toner according to claim 8 or 9, wherein the a-olefin monomer has 16 or more carbon atoms.

[11] The electrostatic image developing toner according to any one of [1] to [10], wherein another aliphatic releasing agent is used in combination with the aliphatic hydrocarbon polymer.

[12] The release agent is

 (1) an aliphatic hydrocarbon polymer having a peak top molecular weight of 10,000 or more and a melting point of 70 ° C or less, and

 (2) Low molecular weight wax with a peak top molecular weight of 5,000 or less

 12. The electrostatic image developing toner according to claim 1, wherein the toner is an electrostatic charge image.

 [13] The electrostatic image developing toner according to [12], which is an ester wax.

14. The electrostatic image developing toner according to claim 12 or 13, wherein the aliphatic hydrocarbon polymer has a melting point (TmD) equal to or lower than the melting point (TmD) of the low molecular weight wax.

[15] The content ratio of the aliphatic hydrocarbon polymer to the low molecular weight wax (the content of the aliphatic hydrocarbon polymer Z the content of the low molecular weight wax) has a force of 98Z2 to 25Z75. Item 15. The electrostatic image developing toner according to any one of Items 12 to 14.

[16] The electrostatic image developing toner according to any one of [1] to [15], wherein the colored resin particles are produced by a wet method.

17. The electrostatic image developing toner according to any one of claims 1 to 16, wherein the colored resin particles have a core-shell type structure.